CN117800527A - Recycling treatment method for diethyl maleate process wastewater - Google Patents
Recycling treatment method for diethyl maleate process wastewater Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 64
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 title claims abstract description 43
- 238000004064 recycling Methods 0.000 title claims abstract description 21
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 54
- 239000011734 sodium Substances 0.000 claims abstract description 54
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 54
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 17
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 79
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical group CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 20
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 abstract description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 11
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 abstract description 11
- 239000011976 maleic acid Substances 0.000 abstract description 11
- 239000002455 scale inhibitor Substances 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 6
- 239000002912 waste gas Substances 0.000 abstract description 5
- 238000004065 wastewater treatment Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000007787 solid Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 10
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 8
- 238000005886 esterification reaction Methods 0.000 description 6
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 6
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- MSJMDZAOKORVFC-UAIGNFCESA-L disodium maleate Chemical compound [Na+].[Na+].[O-]C(=O)\C=C/C([O-])=O MSJMDZAOKORVFC-UAIGNFCESA-L 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000006735 epoxidation reaction Methods 0.000 description 4
- 239000001530 fumaric acid Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
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- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- -1 maleic monoester Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 229940074369 monoethyl fumarate Drugs 0.000 description 1
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- 230000002441 reversible effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
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Abstract
The application relates to the technical field of maleic acid-containing wastewater treatment, in particular to a method for recycling process wastewater of diethyl maleate, which comprises the following steps: firstly, carrying out hydrolysis reaction and dealcoholization treatment on diethyl maleate process wastewater to obtain dealcoholization wastewater; and mixing a proper amount of maleic anhydride with dealcoholized wastewater to synthesize a sodium polyepoxysuccinate solution, wherein the sodium polyepoxysuccinate is a scale inhibitor with double effects of scale and corrosion inhibition, and has huge market demands. The treatment process has simple steps, does not need high-cost environment-friendly treatment equipment and material investment, can directly sell in a liquid form, does not generate secondary wastewater and waste gas in the whole process, and realizes high environmental protection and good economical efficiency of treatment of the diethyl maleate process wastewater.
Description
Technical Field
The application relates to the technical field of maleic acid-containing wastewater treatment, in particular to a method for recycling process wastewater of diethyl maleate.
Background
Diethyl maleate is an important basic chemical raw material and has important value in the aspects of pesticides and synthetic resins. The preparation method of the diethyl maleate generally adopts maleic anhydride, maleic acid or a mixture containing maleic anhydride and maleic acid to prepare the diethyl maleate through catalytic esterification with ethanol. In view of process and cost considerations, the main stream processes at present all adopt maleic anhydride as a starting material, and the production is carried out by a batch process or a continuous process, and generally comprises two reaction steps of preparing monoethyl maleate by ring-opening half-esterification of maleic anhydride and absolute ethyl alcohol, and then carrying out catalytic di-esterification of the latter with excessive ethyl alcohol. The first half-esterification reaction can be completely reacted under mild conditions without the existence of a catalyst, and the obtained maleic acid monoethyl ester needs to be continuously subjected to the di-esterification reaction with excessive ethanol under the catalysis of strong acid. However, the second reaction is a reversible reaction, and water generated in the system is required to be continuously separated to promote the esterification reaction to move forward, the reaction yield is usually about 95% at most, and the impurities in the product are mainly monoethyl maleate, and also include a small amount of monoethyl fumarate, diethyl fumarate, maleic acid, fumaric acid and the like. In addition, the reaction system also contains excessive alcohol and water. In practice, however, the impurities are removed by purification, except that the excess alcohol is mostly recovered for recycling. The catalyst (such as sulfuric acid, sulfonic acid, etc.), maleic monoester, maleic acid, fumaric acid monoester, etc. can be removed in the steps of alkali washing and water washing, and the treated process waste water mainly contains the excessive alkali (mainly sodium carbonate), the neutralization salt of the catalyst and mixed carboxylate, and also contains a small amount of dissolved or mixed diethyl maleate, the solubility of the diethyl maleate in water is about 2%, and the delamination in the alkali washing process does not thoroughly lead to the diethyl maleate mixed in an oil emulsion state. In general, the total amount of wastewater is about 10% -15% of the production batch.
If a conventional wastewater treatment method is adopted, a multi-stage waste liquid treatment device is needed, and the steps of chemical sedimentation, adsorption filtration, biological fermentation, fenton oxidation, membrane separation and the like are included. Not only is the investment of wastewater treatment equipment and treatment materials required, and complicated daily maintenance is increased, but also the treated bottom mud still needs to be treated as pollution waste residues, and the treatment cost is further increased.
Patent publication No. CN111689848B discloses a method for recycling and purifying waste water containing maleic acid, which comprises the steps of isomerizing maleic acid in the waste water into fumaric acid through a catalytic reaction, separating to obtain a fumaric acid product, and treating the three wastes through an anaerobic pyrolysis device. However, the treatment process is complex, and a small amount of waste gas and waste water can be discharged after the treatment is finished, so that secondary pollution is caused.
Disclosure of Invention
The invention aims to solve the problems that the treatment process of the maleic acid wastewater is complex, and a small amount of waste gas and waste water are discharged after the treatment is finished.
On one hand, the method for recycling the process wastewater of the diethyl maleate adopts the following technical scheme:
a method for recycling treatment of diethyl maleate process wastewater comprises the following steps:
s1: adding sodium hydroxide accounting for 1.0-2.0% of the mass of the waste water into the diethyl maleate process waste water, stirring and dissolving, heating to 45-65 ℃ and carrying out hydrolysis reaction for 1-2 h;
s2: vacuum-pumping the wastewater hydrolyzed in the step S1 for dealcoholization for 0.5 to 1 hour under the condition of keeping the temperature of 45 to 65 ℃ to obtain dealcoholized wastewater;
s3: adding 90-100 parts of maleic anhydride into a reaction kettle according to weight percentage, slowly adding 320-350 parts of dealcoholized wastewater in the step S2 under the condition of keeping stirring, and then adding 140-145 parts of 50% NaOH solution by mass concentration for hydrolysis reaction for 0.5-1 h to obtain a solution a;
s4: adding 10-15 parts of catalyst into the solution a, uniformly stirring, slowly dropwise adding a hydrogen peroxide solution with the mass concentration of 50%, controlling the temperature to 65-70 ℃ after the dropwise adding is finished, and carrying out heat preservation reaction for 12-20 h to obtain a solution b;
s5: adding 4-6 parts of initiator into the solution b, uniformly stirring, adding 10-20 parts of NaOH solution with the mass concentration of 50%, controlling the temperature to 85-90 ℃, adding 6-12 parts of glycol, heating to 90-105 ℃, and carrying out heat preservation reaction for 3-6 hours to obtain the sodium polyepoxysuccinate solution.
In the treatment of the diethyl maleate process wastewater, the diethyl maleate process wastewater is generally required to be treated by a wastewater treatment plant in order to pay cost, the industry can not reuse, the hydrolyzed and dealcoholized diethyl maleate process wastewater is used as a raw material to synthesize the sodium polyepoxysuccinate, and the synthesized sodium polyepoxysuccinate is a scale inhibitor with double effects of scale inhibition and corrosion inhibition, and has huge market demands, so that the sodium polyepoxysuccinate is one of innovation points of the application; secondly, if the sodium polyepoxysuccinate is synthesized only by the treated wastewater, the solid content of the obtained solution is lower and can not reach the solid content of the standard scale inhibitor, and secondary treatment is also needed.
In the application, sodium hydroxide is added into diethyl maleate process wastewater, diethyl maleate and monoethyl maleate in the wastewater undergo hydrolysis reaction under alkaline conditions to obtain sodium maleate and ethanol, and then the generated alcohol is removed by vacuumizing and dealcoholizing to obtain dealcoholized wastewater. In the step S3, maleic anhydride is hydrolyzed under the action of NaOH solution to obtain sodium maleate; in step S4, sodium maleate is oxidized by hydrogen peroxide under the catalysis condition to generate sodium epoxy succinate; in the step S5, the sodium epoxy succinate is subjected to polymerization reaction under the action of an initiator to obtain sodium polyepoxysuccinate, wherein ethylene glycol can play a role of a polymerization initiator and a chain transfer agent in the polymerization reaction, and the rate of the polymerization reaction and the molecular weight distribution of the sodium polyepoxysuccinate can be regulated, so that the performance of the sodium polyepoxysuccinate is improved. The treatment process has simple steps, does not need high-cost environment-friendly treatment equipment and material investment, can directly sell in a liquid form, does not generate secondary wastewater and waste gas in the whole process, and realizes high environmental protection and good economical efficiency of treatment of the diethyl maleate process wastewater.
In the step S4, the catalyst is sodium tungstate dihydrate.
By adopting the technical scheme, the sodium tungstate dihydrate is used as a catalyst, has good catalytic activity, can promote the epoxidation reaction of maleic acid, and improves the reaction rate.
Optionally, in H 2 O 2 The addition amount of the hydrogen peroxide is 1.2 to 1.5 times of the molar amount of the maleic anhydride.
By adopting the technical scheme, part of hydrogen peroxide can be decomposed in the epoxidation reaction process to generate water and oxygen; therefore, the excessive hydrogen peroxide is added, so that the reaction can be fully carried out, the yield and purity of the polyepoxysuccinate sodium are improved, and the scale inhibition performance of the polyepoxysuccinate sodium is improved.
Optionally, the initiator is calcium hydroxide.
By adopting the technical scheme, the calcium hydroxide can effectively initiate the polymerization reaction, and the reaction rate and the reaction efficiency are improved, so that the reaction can be completed in a shorter time.
Optionally, in the step S3, naOH solution is added to adjust the pH of the reaction solution to 5.0 to 7.0.
By adopting the technical scheme, when the maleic anhydride and the monoethyl maleate in the wastewater undergo hydrolysis reaction, a large amount of acid can be generated, so that the pH value of the solution is reduced; in the epoxidation reaction of step S4, too low a pH value activates the epoxy group in the sodium epoxysuccinate, which is easily ring-opened by the addition of water, alcohol, carboxylic acid, etc. to obtain tartaric acid or a by-product of similar structure, while too high a pH value causes a large amount of hydrogen peroxide to decompose into oxygen and water, so that the pH value of the reaction solution is adjusted to be weakly acidic or neutral, and the yield of the product can be improved.
Optionally, in the step S5, naOH solution is added to adjust the pH of the reaction solution to 12.0 or higher.
By adopting the technical scheme, in the synthesis process of the polyepoxysuccinate, the polymerization reaction can be promoted in an overbased environment, and the side reaction can be restrained, so that the yield and purity of the product are improved.
Optionally, the mass percentage of the maleic acid monoester and the maleic acid diethyl ester in the maleic acid diethyl ester process wastewater is 8-12%.
On the other hand, the sodium polyepoxysuccinate solution provided by the application adopts the following technical scheme:
the sodium polyepoxysuccinate solution is obtained by the recycling treatment method.
By adopting the technical scheme, the sodium polyepoxysuccinate can be efficiently synthesized by utilizing the recycling treatment method, the cost of the scale inhibitor is reduced, and the recycling of resources is realized.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the treatment process has simple steps, does not need high-cost environment-friendly treatment equipment and material investment, can directly sell the obtained product in a liquid form, does not generate secondary waste water and waste gas in the whole process, and realizes high environmental protection and good economical efficiency of treatment of the diethyl maleate process waste water;
2. during the epoxidation reaction, part of the hydrogen peroxide is decomposed to produce water and oxygen; therefore, the excessive hydrogen peroxide is added, so that the reaction can be fully carried out, the yield and purity of the polyepoxysuccinate sodium are improved, and the scale inhibition performance of the polyepoxysuccinate sodium is improved; 3. by utilizing the recycling treatment method, the polyepoxysuccinate sodium can be efficiently synthesized, the cost of the scale inhibitor is reduced, and the recycling of resources is realized.
Detailed Description
For the sake of brevity, the articles used in the following examples are all commercial products unless otherwise specified, and the methods used are all conventional methods unless otherwise specified.
The present application is described in further detail below in connection with examples and comparative examples.
Examples
Example 1
The preparation method of the polyepoxysuccinate sodium solution provided by the embodiment comprises the following steps:
s1: adding 800g of diethyl maleate process wastewater and 8g of sodium hydroxide into a 1L three-neck flask, fully stirring and dissolving, heating to 65 ℃, carrying out hydrolysis reaction for 2 hours, and hydrolyzing until the surface of the solution has no layering and no oil bead turbidity;
s2: vacuumizing and dealcoholizing the hydrolyzed wastewater for 1h under the condition of keeping 65 ℃ to obtain dealcoholized wastewater;
s3: adding 98g of maleic anhydride into the other 1L three-neck flask, slowly adding 320g of dealcoholized wastewater under the condition of keeping stirring, adding 140g of 50% NaOH solution by mass concentration, adjusting the pH value to 7.0, and carrying out hydrolysis reaction for 1h to obtain a solution a;
s4: adding 12g of catalyst into the solution a, uniformly stirring, slowly dropwise adding 100g of hydrogen peroxide solution with the mass concentration of 50%, controlling the temperature to 70 ℃ after the dropwise adding is finished, and carrying out heat preservation reaction for 15h to obtain a solution b;
s5: adding 5g of calcium hydroxide into the solution b, uniformly stirring, adding 16g of 50% NaOH solution, adjusting the pH to be more than 12.0, controlling the temperature to 90 ℃, adding 8g of ethylene glycol, then heating to 95 ℃, and carrying out heat preservation reaction for 5 hours to obtain the sodium polyepoxysuccinate solution.
Example 2
This embodiment differs from embodiment 1 in that: in the step S1, the addition amount of sodium hydroxide was 12g.
Example 3
This embodiment differs from embodiment 1 in that: in the step S3, the addition amount of sodium hydroxide was 16g.
Example 4
This embodiment differs from embodiment 2 in that: in the step S3, the addition amount of the dealcoholized wastewater is 290g.
Example 5
This embodiment differs from embodiment 2 in that: in the step S3, the addition amount of the dealcoholized wastewater is 350g.
Example 6
This embodiment differs from embodiment 2 in that: in the step S5, the addition amount of the ethylene glycol is 6g.
Example 7
This embodiment differs from embodiment 2 in that: in the step S5, the addition amount of ethylene glycol is 10g.
Example 8
This embodiment differs from embodiment 2 in that: in the step S5, the addition amount of the ethylene glycol is 12g.
Comparative example
Comparative example 1
The preparation method of the polyepoxysuccinate sodium solution provided by the embodiment comprises the following steps:
s3: adding 98g of maleic anhydride into another 1L three-neck flask, slowly adding 320g of dealcoholized wastewater under the condition of stirring, adding 140g of 50% NaOH solution by mass concentration, adjusting the pH value to 7, and carrying out hydrolysis reaction for 1h to obtain a solution a; s4: adding 12g of catalyst into the solution a, uniformly stirring, slowly dropwise adding 100g of hydrogen peroxide solution with the mass concentration of 50%, controlling the temperature to 70 ℃ after the dropwise adding is finished, and carrying out heat preservation reaction for 15h to obtain a solution b;
s5: adding 5g of calcium hydroxide into the solution b, uniformly stirring, adding 16g of 50% NaOH solution, adjusting the pH to be more than 12, controlling the temperature to 90 ℃, adding 8g of ethylene glycol, heating to 95 ℃, and carrying out heat preservation reaction for 5h to obtain the sodium polyepoxysuccinate solution.
Comparative example 2
The preparation method of the polyepoxysuccinate sodium solution provided by the embodiment comprises the following steps:
s1: adding 800g of diethyl maleate process wastewater and 12g of sodium hydroxide into a 1L three-neck flask, fully stirring and dissolving, heating to 65 ℃, carrying out hydrolysis reaction for 2 hours, and hydrolyzing until the surface of the solution has no layering and no oil bead turbidity;
s2: vacuumizing and dealcoholizing the hydrolyzed wastewater for 1h under the condition of keeping 65 ℃ to obtain dealcoholized wastewater;
s3: adding 98g of deionized water into another 1L three-neck flask, slowly adding 320g of dealcoholized wastewater under the condition of stirring, adding 50% NaOH solution, adjusting the pH value to 7, and carrying out hydrolysis reaction for 1h to obtain a solution a;
s4: adding 12g of catalyst into the solution a, uniformly stirring, slowly dropwise adding 100g of hydrogen peroxide solution with the mass concentration of 50%, controlling the temperature to 70 ℃ after the dropwise adding is finished, and carrying out heat preservation reaction for 15h to obtain a solution b;
s5: adding 5g of calcium hydroxide into the solution b, uniformly stirring, adding a NaOH solution with the mass concentration of 50%, regulating the pH to be more than 12, controlling the temperature to 90 ℃, adding 8g of ethylene glycol, then heating to 95 ℃, and carrying out heat preservation reaction for 5 hours to obtain the sodium polyepoxysuccinate solution.
Comparative example 3
The present comparative example differs from example 2 in that: in the step S5, the addition amount of ethylene glycol is 0.
In order to intuitively present the formulation data of all examples and comparative examples, table 1 is specially formulated as follows:
table 1: recipe data for examples 1-8 and comparative examples 1-3
Performance testing
The following performance tests were carried out on the sodium polyepoxysuccinate solutions provided in examples 1 to 8 and comparative examples 1 to 3 according to the present application, and the specific test results are shown in Table 2.
1. Solid content
The method for detecting the solid content is a drying method, the weight of the finally obtained polyepoxysuccinate sodium solution (total weight of the solution) is weighed, the solution is placed in a constant temperature and humidity box, the solution is allowed to lose moisture at a certain temperature and for a certain time, the weight of the remainder (weight of solid) is weighed, and the solid content is calculated according to the weight of the solution and the weight of the remainder.
The specific calculation mode is as follows:
solution solids content = weight of residue/solutionThe weight of the liquid was multiplied by 100%.
2. Scale inhibition rate
The scale inhibition rate test is carried out on the polyepoxysuccinate sodium solution according to the standard of GB/T16632-2019 water treatment agent scale inhibition performance measurement calcium carbonate deposition method.
Note that: the amount of scale inhibitor tested was 10mg/L, calculated as the weight of solids in the sodium polyepoxysuccinate solution.
Table 2: results of Performance test of examples 1 to 8 and comparative examples 1 to 3
| Examples | Solids content/% | Scale inhibition/% |
| Example 1 | 43.1 | 95.6 |
| Example 2 | 45.4 | 100.0 |
| Example 3 | 45.2 | 100.0 |
| Example 4 | 42.8 | 99.5 |
| Example 5 | 45.9 | 97.2 |
| Example 6 | 44.4 | 97.0 |
| Example 7 | 44.9 | 97.3 |
| Example 8 | 44.1 | 95.0 |
| Comparative example 1 | 37.9 | 86.5 |
| Comparative example 2 | 25.5 | 93.9 |
| Comparative example 3 | 40.5 | 91.1 |
Referring to tables 1 to 2, in combination with the detection results of examples 1 to 3, it is understood that the addition amount of different sodium hydroxide affects the performance of sodium polyepoxysuccinate in the hydrolysis reaction of diethyl maleate process wastewater. The sodium hydroxide is added, so that the diethyl maleate in the diethyl maleate process wastewater can be subjected to hydrolysis reaction to produce sodium maleate and ethanol, and if the addition amount of the sodium hydroxide is too small, the hydrolysis reaction is insufficient, so that the solid content and the scale inhibition performance of the sodium polyepoxysuccinate are affected; in example 3, however, the amount of sodium hydroxide added was large, and the improvement in the properties of the product was not large. From this, it was found that when the amount of sodium hydroxide added was 12g, diethyl maleate was sufficiently hydrolyzed, and the obtained sodium epoxysuccinate was excellent in solid content and scale inhibition properties.
In addition, the detection results of comparative example 2 and comparative example 1 further demonstrate that the solid content of sodium polyepoxysuccinate can be effectively increased by adding sodium hydroxide to carry out hydrolysis and dealcoholization prior to the synthesis reaction of sodium polyepoxysuccinate. In comparative example 1, although the diethyl maleate process wastewater was not subjected to hydrolysis treatment, the subsequent reaction was performed by adding a sodium hydroxide solution, and the diethyl maleate was also subjected to hydrolysis reaction, so that the solid content of the final product could still reach 37.9%, but since the dealcoholization treatment was not performed, a large amount of alcohol was mixed in the sodium polyepoxysuccinate solution, thereby affecting the scale inhibition performance of sodium polyepoxysuccinate.
As can be seen from the results of the tests in examples 2, 4 and 5, by adjusting the amount of the dealcoholized wastewater, sodium polyepoxysuccinate solutions with different solid contents can be obtained; when the addition amount of the dealcoholized wastewater is 320g, the solid content of the obtained polyepoxysuccinate sodium solution is 45.4%, the standard of the commercial scale inhibitor is achieved, and the scale inhibition performance is also optimal. In example 5, however, the scale inhibition performance of the sodium polyepoxysuccinate solution was lowered as compared with example 2, because the dealcoholized wastewater was not completely reacted, and impurities were mixed in the product, thereby affecting the scale inhibition performance of the sodium polyepoxysuccinate.
In addition, as is clear from the detection results of comparative examples 2 and 2, the solid content of the product of the synthesis of sodium polyepoxysuccinate by replacing maleic anhydride with deionized water and using only dealcoholized wastewater as a raw material is far from the commercial standard, and secondary treatment is required to adjust the solid content of the sodium polyepoxysuccinate solution.
The detection results of examples 2 and 6-8 are combined, and it is known that in the polymerization reaction of sodium epoxy succinate, ethylene glycol is added, and can play a role of a polymerization initiator and a chain transfer agent, and can adjust the rate of the polymerization reaction and the molecular weight distribution of the sodium polyepoxysuccinate, so that the scale inhibition performance of the sodium polyepoxysuccinate is improved, and the efficiency of the polymerization reaction is improved. In example 6, the amount of ethylene glycol added was small, and the properties of the obtained product were inferior to those of example 2, probably because, when the amount of ethylene glycol added was insufficient, it might result in incomplete polymerization, so that the molecular weight of the product was lowered, and at the same time, it was difficult to control the polymerization process, resulting in lowered properties; in examples 7 to 8, when the amount of ethylene glycol added is large, the molecular weight distribution of the produced sodium polyepoxysuccinate may be too broad, and the molecular weight may be too low, which may affect the stability of the product and thus the scale inhibition of the sodium epoxysuccinate solution. From this, it was found that when the amount of ethylene glycol added was 8g, the scale inhibition performance of the obtained sodium polyepoxysuccinate solution was optimal.
In addition, the detection results of comparative examples 2 and 3 further demonstrate that ethylene glycol can effectively promote the polymerization reaction, improve the solid content of the sodium polyepoxysuccinate solution, and optimize the molecular weight and molecular weight distribution of the sodium polyepoxysuccinate, thereby improving the scale inhibition performance.
In summary, in all the embodiments of the present application, the best embodiment is embodiment 2, the solid content of the prepared polyepoxysuccinate solution is 45.4%, the scale inhibition rate is 100.0%, the scale inhibitor meets the standard of the commercial scale inhibitor, the scale inhibitor can be directly sold in a liquid form, secondary treatment is not needed, the cost is lower, and the high environmental protection and good economical efficiency of the treatment of the waste water of the diethyl maleate process are realized.
The embodiments of the present invention are all preferred embodiments of the present application, and are not intended to limit the scope of the present application. Therefore: all equivalent changes in structure, shape and principle of this application should be covered in the protection scope of this application.
Claims (8)
1. A method for recycling treatment of diethyl maleate process wastewater is characterized by comprising the following steps:
s1: adding sodium hydroxide accounting for 1.0-2.0% of the mass of the waste water into the diethyl maleate process waste water, stirring and dissolving, heating to 45-65 ℃ and carrying out hydrolysis reaction for 1-2 h;
s2: vacuum-pumping the wastewater hydrolyzed in the step S1 for dealcoholization for 0.5 to 1 hour under the condition of keeping the temperature of 45 to 65 ℃ to obtain dealcoholized wastewater;
s3: adding 90-100 parts of maleic anhydride into a reaction kettle according to weight percentage, slowly adding 320-350 parts of dealcoholized wastewater in the step S2 under the condition of keeping stirring, and then adding 140-145 parts of 50% NaOH solution by mass concentration for neutralization reaction for 0.5-1 h to obtain a solution a;
s4: adding 10-15 parts of catalyst into the solution a, uniformly stirring, slowly dropwise adding a hydrogen peroxide solution with the mass concentration of 30% -50%, controlling the temperature to 65-70 ℃ after the dropwise adding is finished, and carrying out heat preservation reaction for 12-20 h to obtain a solution b;
s5: adding 4-6 parts of initiator into the solution b, uniformly stirring, adding 10-20 parts of NaOH solution with the mass concentration of 50%, controlling the temperature to 85-90 ℃, adding 6-12 parts of glycol, heating to 90-105 ℃, and carrying out heat preservation reaction for 3-6 hours to obtain the sodium polyepoxysuccinate solution.
2. The method for recycling the diethyl maleate process wastewater according to claim 1, wherein in the step S4, the catalyst is sodium tungstate dihydrate.
3. The method for recycling the diethyl maleate process wastewater according to claim 1, wherein H is used for 2 O 2 The addition amount of the hydrogen peroxide is 1.2 to 1.5 times of the molar amount of the maleic anhydride.
4. The method for recycling the diethyl maleate process wastewater according to claim 1, wherein the initiator is calcium hydroxide.
5. The method for recycling the diethyl maleate process wastewater according to claim 4, wherein in the step S3, naOH solution is added to adjust the pH value of the reaction solution to 5.0-7.0.
6. The method for recycling the diethyl maleate process wastewater according to claim 1, wherein in the step S5, naOH solution is added to adjust the pH of the reaction solution to 12.0 or higher.
7. The recycling treatment method of the diethyl maleate process wastewater according to claim 1, wherein the total mass percentage of the maleic monoester and the diethyl maleate in the diethyl maleate process wastewater is 8% -12%.
8. A sodium polyepoxysuccinate solution obtainable by a recycling process according to any one of claims 1 to 7.
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